Highly viscous microemulsions based on sugar surfactants, oily bodies and aluminium salts and the use thereof in the production of anti-perspirant gel and stick preparations

ABSTRACT

A highly-viscous microemulsion containing: (a) a sugar surfactant; (b) an oil component; and (c) an aluminium-zirconium salt, and wherein the composition is transparent and has a Brookfield viscosity of at least about 100,000 mPas.

FIELD OF THE INVENTION

[0001] This invention relates generally to cosmetic emulsions and moreparticularly to high-viscosity microemulsions based on sugarsurfactants, oil components and aluminium-zirconium salts and to theiruse for the production of cosmetic gel and stick formulations.

PRIOR ART

[0002] Microemulsions are optically isotropic, thermodynamically stablesystems which contain a water-insoluble oil component, emulsifiers andwater. The clear or transparent appearance of microemulsions is a resultof the small particle size of the dispersed emulsion droplets which, forthe most part, is under 300 nm, fine-droplet microemulsions brown-red intransmitted light and a shimmering blue in reflected light occurring inthe 100 to 300 nm range and optically clear microemulsions occurring inthe sub-100 nm range. The droplet size of the macroemulsions is for themost part above 300 nm. By virtue of their greater stability in relationto macroemulsions, the finer distribution of the inner phase, theirgenerally greater effectiveness and the better transdermal penetrationof the active principles incorporated therein, microemulsions haveacquired considerable significance in the formulation of cosmetic andpharmaceutical preparations. However, their use in water-containingcosmetic gel and stick preparations which can be found on the market asantiperspirant or deodorant products requires a high consistency.Establishing the viscosity of such a system with long-chain polymersoften results in loss of the required transparency or in displacement ofthe thermodynamic equilibrium. Conventional thickeners, mainly polymers,leave the skin feeling sticky after application of the formulationscontaining them. In addition, antiperspirant or deodorant products areformulated at an acidic pH of ca. 4 and, to this end, require thickenersystems that are stable in this pH range, for example polydiols incombination with dibenzylidene sorbitol.

[0003] In addition, various antiperspirant sticks based on natural orsynthetic waxes in which the active substance is introduced into the waxmatrix as a powder have been available on the market for many years. Thedisadvantage of such sticks is that they are very greasy and often leavea white residue on the skin.

[0004] The complex problem addressed by the present invention was toprovide high-viscosity microemulsions which would be distinguished bytransparency and high stability and which could be used asantiperspirant gel or stick formulations without the adverse sensoryeffects of large quantities of polymeric thickeners. Oily and aqueoussolutions would lend themselves to processing in the formulation,thereby simplifying homogeneous distribution.

DESCRIPTION OF THE INVENTION

[0005] The present invention relates to high-viscosity microemulsionscontaining

[0006] A) sugar surfactants,

[0007] B) oil components and

[0008] C) aluminium-zirconium salts.

[0009] It has surprisingly been found that the combination of sugarsurfactants, oil components and aluminium-zirconium salts leads to cleartransparent microemulsions with viscosities of at least 100,000 mPas,preferably 400,000 mPas and more particularly 800,000 to 3,000,000 mPas.

[0010] Besides their stability and transparency, the formulationsaccording to the invention have a consistency which enables them to beprocessed into gels or sticks. Conventional polymeric thickeners, whichare attended by the disadvantage that they leave the skin feelingsticky, can be reduced or even avoided altogether. Oily and aqueoussolutions can be processed in the formulation so that homogeneousdistribution is simplified.

Sugar Surfactants

[0011] Sugar surfactants are surface-active substances based oncarbohydrates which include, for example, sugar esters, sorbitan estersand polysorbates, alkyl oligoglucosides and fatty acid glucamides. Sugaresters are esters of mono- and oligosaccharides and—in the broadersense—of sugar alcohols with organic and inorganic acids. Industriallythe most important sugar esters are the mono- and diesters of thesugars, more especially sucrose, with higher fatty acids, such aslauric, myristic, palmitic, stearic or oleic acid or with tallow fattyacids. These sugar esters have pronounced surface-active properties [cf.Römpp Lexikon Chemie—Version 2.0, Stuttgart/New York; Georg ThiemeVerlag 1999]. Sorbitan esters are mono-, di- and triesters of thesorbitans with fatty acids. Sorbitan esters and their ethoxylatedderivatives (polysorbates) are used as particularly environmentally safenonionic surfactants in the cosmetics, pharmaceutical and foodindustries [cf. J. Am. Oil Chem. Soc. 66, 1581 (1989), Tenside Surf.Deterg. 27, 350 (1990)].

Alkyl and/or Alkenyl Oligoglycosides

[0012] Alkyl and alkenyl oligoglycosides suitable as emulsifiercomponent are known nonionic surfactants which correspond to generalformula (I):

R¹O-[G]_(p)  (I)

[0013] where R¹ is an alkyl and/or alkenyl group containing 4 to 22carbon atoms, G is a sugar unit containing 5 or 6 carbon atoms and p isa number of 1 to 10. They may be obtained by the relevant methods ofpreparative organic chemistry. EP-A1-0 301 298 and WO 90/03977 are citedas representative of the extensive literature available on this subject.

[0014] The alkyl and/or alkenyl oligoglycosides may be derived fromaldoses or ketoses containing 5 or 6 carbon atoms, preferably glucose.The index p in general formula (I) indicates the degree ofoligomerization (DP), i.e. the distribution of mono- andoligoglycosides, and is a number of 1 to 10. Whereas p in a givencompound must always be an integer and, above all, may assume a value of1 to 6, the value p for a certain alkyl oligoglycoside is ananalytically determined calculated quantity which is generally a brokennumber. Alkyl and/or alkenyl oligoglycosides having an average degree ofoligomerization p of 1.1 to 3.0 are preferably used. Alkyl and/oralkenyl oligoglycosides having a degree of oligomerization of less than1.7 and, more particularly, between 1.2 and 1.4 are preferred from theapplicational point of view.

[0015] The alkyl or alkenyl group R¹ may be derived from primaryalcohols containing 4 to 11 and preferably 8 to 10 carbon atoms. Typicalexamples are butanol, caproic alcohol, caprylic alcohol, capric alcoholand undecyl alcohol and the technical mixtures thereof obtained, forexample, in the hydrogenation of technical fatty acid methyl esters orin the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyloligoglucosides having a chain length of C₈ to C₁₀ (DP=1 to 3), whichare obtained as first runnings in the separation of technical C₈₋₁₈coconut oil fatty alcohol by distillation and which may contain lessthan 6% by weight of C₁₂ alcohol as an impurity, and also alkyloligoglucosides based on technical C_(9/11) oxoalcohols (DP=1 to 3) arepreferred. In addition, the alkyl or alkenyl group R¹ may also bederived from primary alcohols containing 12 to 22 and preferably 12 to14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol,cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol,oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol,gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol andtechnical mixtures thereof which may be obtained as described above.Alkyl oligoglucosides based on hydrogenated C_(12/14) coconut oil fattyalcohol having a DP of 1 to 3 are preferred.

Fatty Acid-N-Alkyl Polyhydroxyalkylamides

[0016] Fatty acid-N-alkyl polyhydroxyalkylamides are nonionicsurfactants corresponding to formula (II):

[0017] in which R²CO is an aliphatic acyl group containing 6 to 22carbon atoms, R³ is hydrogen, an alkyl or hydroxyalkyl group containing1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkylgroup containing 3 to 12 carbon atoms and 3 to 10 hydroxyl groups. Thefatty acid-N-alkyl polyhydroxyalkylamides are known compounds which maynormally be obtained by reductive amination of a reducing sugar withammonia, an alkylamine or an alkanolamine and subsequent acylation witha fatty acid, a fatty acid alkyl ester or a fatty acid chloride.Processes for their production are described in U.S. Pat. No. 1,985,424,in U.S. Pat. No. 2,016,962 and in U.S. Pat. No. 2,703,798 and inInternational patent application WO 92/06984. An overview of thissubject by H. Kelkenberg can be found in Tens. Surf. Det. 25, 8 (1988).

[0018] The fatty acid-N-alkyl polyhydroxyalkylamides are preferablyderived from reducing sugars containing 5 or 6 carbon atoms, moreparticularly from glucose. Accordingly, the preferred fatty acid-N-alkylpolyhydroxyalkylamides are fatty acid-N-alkyl glucamides whichcorrespond to formula (III):

[0019] Preferred fatty acid-N-alkyl polyhydroxyalkylamides areglucamides corresponding to formula (III) in which R³ is hydrogen or analkyl group and R²CO represents the acyl component of caproic acid,caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid,palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidicacid, petroselic acid, linoleic acid, linolenic acid, arachic acid,gadoleic acid, behenic acid or erucic acid or technical mixturesthereof. Fatty acid-N-alkyl glucamides (III) obtained by reductiveamination of glucose with methylamine and subsequent acylation withlauric acid or C_(12/14) coconut oil fatty acid or a correspondingderivative are particularly preferred. In addition, thepolyhydroxyalkylamides may also be derived from maltose and palatinose.

Oil Components

[0020] Suitable oil components are, for example, Guerbet alcohols basedon fatty alcohols containing 6 to 18 and preferably 8 to 10 carbonatoms, esters of linear C₆₋₂₂ fatty acids with linear C₆₋₂₂ fattyalcohols, esters of branched C₆₋₁₃ carboxylic acids with linear C₆₋₂₂fatty alcohols such as, for example, myristyl myristate, myristylpalmitate, myristyl stearate, myristyl isostearate, myristyl oleate,myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate,cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetylerucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearylisostearate, stearyl oleate, stearyl behenate, stearyl erucate,isostearyl myristate, isostearyl palmitate, isostearyl stearate,isostearyl isostearate, isostearyl oleate, isostearyl behenate,isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate,oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenylmyristate, behenyl palmitate, behenyl stearate, behenyl isostearate,behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate,erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate,erucyl behenate and erucyl erucate. Also suitable are esters of linearC₆₋₂₂ fatty acids with branched alcohols, more particularly 2-ethylhexanol, esters of C₁₈₋₃₈ alkylhydroxy-carboxylic acids with linear orbranched C₆₋₂₂ fatty alcohols (cf. DE 197 56 377 A1), more especiallyDioctyl Malate, esters of linear and/or branched fatty acids withpolyhydric alcohols (for example propylene glycol, dimer diol or trimertriol) and/or Guerbet alcohols, triglycerides based on C₆₋₁₀ fattyacids, liquid mono-, di- and triglyceride mixtures based on C₆₋₁₈ fattyacids, esters of C₆₋₂₂ fatty alcohols and/or Guerbet alcohols witharomatic carboxylic acids, more particularly benzoic acid, esters ofC₂₋₁₂ dicarboxylic acids with linear or branched alcohols containing 1to 22 carbon atoms or polyols containing 2 to 10 carbon atoms and 2 to 6hydroxyl groups, vegetable oils, branched primary alcohols, substitutedcyclohexanes, linear and branched C₆₋₂₂ fatty alcohol carbonates,Guerbet carbonates, esters of benzoic acid with linear and/or branchedC₆₋₂₂ alcohols (for example Finsolv® TN), linear or branched,symmetrical or nonsymmetrical dialkyl ethers containing 6 to 22 carbonatoms per alkyl group, ring opening products of epoxidized fatty acidesters with polyols, silicone oils (cyclomethicone, silicon methiconetypes, etc.) and/or aliphatic or naphthenic hydrocarbons, for examplesqualane, squalene or dialkyl cyclohexanes, dialkyl carbonatescorresponding to formula (IV):

[0021] in which R¹ is a linear alkyl and/or alkenyl group containing 6to 22 carbon atoms, a 2-ethylhexyl, isotridecyl or isostearyl group or agroup derived from a polyol containing 2 to 15 carbon atoms and at leasttwo hydroxyl groups, R² has the same meaning as R¹ or is an alkyl groupcontaining 1 to 5 carbon atoms and n and m independently of one anotherrepresent 0 or numbers of 1 to 100, preferably dioctyl carbonate.

Aluminium-Zirconium Salts

[0022] Salts of aluminium, zirconium or zinc are used as astringentantiperspirants. Aluminium-zirconium salts in particular aredistinguished by good antihydrotic activity. They are preferably complexcompounds of amino acids, for example glycine, with chlorohydrate saltsof the metals aluminium and zirconium in an Al:Zr ratio of 3 to 10:1(ratio of metals to chloride 0.9 to 2.1:1). Aluminium-zirconiumtrichlorohydrate, aluminium-zirconium tetrachlorohydrate,aluminium-zirconium pentachlorohydrate, aluminium-zirconiumoctachlorohydrate are preferably used in cosmetic formulations.

Thickeners

[0023] Suitable thickeners are, for example, polysaccharides, moreespecially xanthan gum, guar-guar, agar-agar, alginates and tyloses,carboxymethyl cellulose and hydroxyethyl cellulose, also relatively highmolecular weight polyethylene glycol monoesters and diesters of fattyacids, polyacrylates, polyvinyl alcohol and polyvinyl pyrrolidone,surfactants such as, for example, ethoxylated fatty acid glycerides,esters of fatty acids with polyols, for example pentaerythritol ortrimethylol propane, narrow-range fatty alcohol ethoxylates or alkyloligoglucosides and electrolytes, such as sodium chloride and ammoniumchloride. However, the advantage of the formulation according to theinvention is that the quantities of thickeners used can be reduced. Ifonly 2% m/m thickener is added to the formulation according to theinvention, an increase in viscosity of up to at least 2,000,000 mPas andpreferably between 2,000,000 and 3,000,000 mPas is achieved.

Co-Emulsifiers

[0024] To prepare microemulsions, sugar surfactants are used incombination with co-emulsifiers of which partial glycerides arepreferably used. The ratio of sugar surfactants to partial glyceridesshould be in the range from 10:90 to 90:10, preferably in the range from20:80 to 80:20 and more particularly in the range from 40:60 to 60:40.

[0025] Suitable co-emulsifiers are, for example, nonionic surfactantsfrom at least one of the following groups:

[0026] products of the addition of 2 to 30 mol ethylene oxide and/or 0to 5 mol propylene oxide onto linear fatty alcohols containing 8 to 22carbon atoms, onto fatty acids containing 12 to 22 carbon atoms and ontoalkylphenols containing 8 to 15 carbon atoms in the alkyl group;

[0027] C_(12/18) fatty acid monoesters and diesters of products of theaddition of 1 to 30 mol ethylene oxide onto glycerol;

[0028] glycerol monoesters and diesters of saturated and unsaturatedfatty acids containing 6 to 22 carbon atoms and ethylene oxide adductsthereof;

[0029] products of the addition of 15 to 60 mol ethylene oxide ontocastor oil and/or hydrogenated castor oil;

[0030] polyol esters and, in particular, polyglycerol esters such as,for example, polyglycerol polyricinoleate or polyglycerolpoly-12-hydroxy-stearate. Mixtures of compounds from several of theseclasses are also suitable;

[0031] products of the addition of 2 to 15 mol ethylene oxide ontocastor oil and/or hydrogenated castor oil;

[0032] partial esters based on linear, branched, unsaturated orsaturated C_(12/22) fatty acids, ricinoleic acid and 12-hydroxystearicacid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol;

[0033] trialkyl phosphates;

[0034] wool wax alcohols;

[0035] polysiloxane/polyalkyl polyether copolymers and correspondingderivatives;

[0036] mixed esters of pentaerythritol, fatty acids, citric acid andfatty alcohol according to DE 1165574 PS and

[0037] polyalkylene glycols;

[0038] mono-, di- and trialkyl phosphates and mono-, di- and/ortri-PEG-alkyl phosphates and salts thereof;

[0039] block copolymers, for example Polyethyleneglycol-30Dipolyhydroxystearate;

[0040] polymer emulsifiers, for example Pemulen types (TR-1, TR-2) fromGoodrich;

[0041] glycerol carbonate.

[0042] The addition products of ethylene oxide and/or propylene oxideonto fatty alcohols, fatty acids, alkylphenols or onto castor oil areknown commercially available products. They are homolog mixtures ofwhich the average degree of alkoxylation corresponds to the ratiobetween the quantities of ethylene oxide and/or propylene oxide andsubstrate with which the addition reaction is carried out. C_(12/18)fatty acid monoesters and diesters of adducts of ethylene oxide withglycerol are known as refatting agents for cosmetic formulations from DE20 24 051 PS.

[0043] Typical examples of suitable partial glycerides arehydroxystearic acid monoglyceride, hydroxystearic acid diglyceride,isostearic acid monoglyceride, isostearic acid diglyceride, oleic acidmonoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride,ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic aciddiglyceride, linolenic acid monoglyceride, linolenic acid diglyceride,erucic acid monoglyceride, erucic acid diglyceride, tartaric acidmonoglyceride, tartaric acid diglyceride, citric acid monoglyceride,citric acid diglyceride, malic acid monoglyceride, malic aciddiglyceride and technical mixtures thereof which may still contain smallquantities of triglyceride from the production process. Additionproducts of 1 to 30 and preferably 5 to 10 mol ethylene oxide onto thepartial glycerides mentioned are also suitable.

[0044] Typical examples of suitable polyglycerol esters arePolyglyceryl-2 Dipolyhydroxystearate (Dehymuls® PGPH), Polyglycerin-3Diisostearate (Lameform® TGI), Polyglyceryl-4 Isostearate (Isolan® GI34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate(Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450),Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate(Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane®NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and PolyglycerylPolyricinoleate (Admul® WOL 1403), Polyglyceryl Dimerate Isostearate andmixtures thereof. Examples of other suitable polyolesters are the mono-,di- and triesters of trimethylolpropane or pentaerythritol with lauricacid, cocofatty acid, tallow fatty acid, palmitic acid, stearic acid,oleic acid, behenic acid and the like optionally reacted with 1 to 30moles of ethylene oxide.

[0045] The preparations may also contain fatty alcohols as an additionalcomponent with co-emulsifying properties. Fatty alcohols in the contextof the invention are understood to be primary aliphatic alcohols, suchas caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capricalcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetylalcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleylalcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol,linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol gadolylalcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol, and thetechnical mixtures thereof obtained, for example in the high-pressurehydrogenation of technical methyl esters based on fats and oils oraldehydes from Roelen's oxosynthesis and as monomer fraction in thedimerization of unsaturated fatty alcohols. Technical fatty alcoholscontaining 12 to 18 carbon atoms, such as coconut fatty alcohol forexample, are preferred. The fatty alcohols may make up from 1 to 35% byweight and preferably from 5 to 30% by weight of the preparations.

[0046] Alternatively, diols may also be used. Typical examples aredodecane-1,12-diol, hexadecane-1,16-diol, 12-hydroxystearyl alcohol andring opening products of epoxidized C₆₋₂₂ olefins with water or polyols,preferably glycerol. The diols may make up from 1 to 35% by weight andpreferably from 5 to 30% by weight of the preparations.

[0047] Other suitable emulsifiers are zwitterionic surfactants.Zwitterionic surfactants are surface-active compounds which contain atleast one quaternary ammonium group and at least one carboxylate and onesulfonate group in the molecule. Particularly suitable zwitterionicsurfactants are the so-called betaines, such as the N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate,N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for examplecocoacylaminopropyl dimethyl ammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethyl carboxymethyl glycinate. The fatty acid amide derivativeknown under the CTFA name of Cocamidopropyl Betaine is particularlypreferred. Ampholytic surfactants are also suitable emulsifiers.Ampholytic surfactants are surface-active compounds which, in additionto a C_(8/18) alkyl or acyl group, contain at least one free amino groupand at least one —COOH or —SO₃H group in the molecule and which arecapable of forming inner salts. Examples of suitable ampholyticsurfactants are N-alkyl glycines, N-alkyl propionic acids,N-alkylaminobutyric acids, N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acidscontaining around 8 to 18 carbon atoms in the alkyl group. Particularlypreferred ampholytic surfactants are N-cocoalkylaminopropionate,cocoacylaminoethyl aminopropionate and C_(12/18) acyl sarcosine. Besidesampholytic emulsifiers, quaternary emulsifiers may also be used, thoseof the esterquat type, preferably methyl-quaternized difatty acidtriethanolamine ester salts, being particularly preferred.

Commercial Applications

[0048] High-viscosity microemulsions may be used in cosmetic gel andstick formulations used as antiperspirants. Antiperspirants are cosmeticformulations which reduce perspiration and hence underarm wetness byinfluencing the activity of the eccrine sweat glands and whichcontribute to a reduction of body odor. Hitherto, antiperspirants havepreferably been formulated as water-free suspensions or aswater-containing solutions or emulsions. Given a suitably highviscosity, however, the microemulsions according to the invention may bedirectly used for processing into gels or sticks. Typically they havethe following composition:

[0049] A) 1-40% m/m, preferably 10-30% m/m and more particularly 15-20%m/m sugar surfactants,

[0050] B) 10-50% m/m, preferably 18-35% m/m and more particularly 20-25%m/m oil components,

[0051] C) 5-40% m/m, preferably 10-30% m/m and more particularly 15-20%m/m aluminium-zirconium salts,

[0052] D) 0-10% m/m, preferably 1-8% m/m and more particularly 2-5% m/mthickeners,

[0053] with the proviso that the quantities shown add up to 100% m/m,optionally with water and/or other typical auxiliaries and additives.

[0054] The preparations according to the invention may containsuperfatting agents, fats, waxes, lecithins, phospholipids, biogenicagents, antioxidants, solubilizers, preservatives, perfume oils, dyesand the like as further auxiliaries and additives.

Fats and Waxes

[0055] Typical examples of fats are glycerides, i.e. solid or liquid,vegetable or animal products which consist essentially of mixed glycerolesters of higher fatty acids. Suitable waxes are inter alia naturalwaxes such as, for example, candelilla wax, carnauba wax, Japan wax,espartograss wax, cork wax, guaruma wax, rice germ oil wax, sugar canewax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin(wool wax), uropygial fat, ceresine, ozocerite (earth wax), petrolatum,paraffin waxes and microwaxes; chemically modified waxes (hard waxes)such as, for example, montan ester waxes, sasol waxes, hydrogenatedjojoba waxes and synthetic waxes such as, for example, polyalkylenewaxes and polyethylene glycol waxes. Besides the fats, other suitableadditives are fat-like substances, such as lecithins and phospholipids.Lecithins are known among experts as glycerophospholipids which areformed from fatty acids, glycerol, phosphoric acid and choline byesterification. Accordingly, lecithins are also frequently referred toby experts as phosphatidyl cholines (PCs) and correspond to generalformula (V):

[0056] where R typically represents linear aliphatic hydrocarbonradicals containing 15 to 17 carbon atoms and up to 4 cis-double bonds.Examples of natural lecithins are the kephalins which are also known asphosphatidic acids and which are derivatives of1,2-diacyl-sn-glycerol-3-phosphoric acids. By contrast, phospholipidsare generally understood to be mono- and preferably diesters ofphosphoric acid with glycerol (glycerophosphates) which are normallyclassed as fats. Sphingosines and sphingolipids are also suitable.

Superfatting Agents

[0057] Superfatting agents may be selected from such substances as, forexample, lanolin and lecithin and also polyethoxylated or acylatedlanolin and lecithin derivatives, polyol fatty acid esters,monoglycerides and fatty acid alkanolamides, the fatty acidalkanolamides also serving as foam stabilizers.

Antioxidants

[0058] Typical examples of suitable antioxidants are amino acids (forexample glycine, histidine, tyrosine, tryptophane) and derivativesthereof, imidazoles (for example urocanic acid) and derivatives thereof,peptides, such as D,L-carnosine, D-carnosine, L-carnosine andderivatives thereof (for example anserine), carotinoids, carotenes (forexample α-carotene, β-carotene, lycopene) and derivatives thereof,chlorogenic acid and derivatives thereof, liponic acid and derivativesthereof (for example dihydroliponic acid), aurothioglucose,propylthiouracil and other thiols (for example thioredoxine,glutathione, cysteine, cystine, cystamine and glycosyl, N-acetyl,methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl,γ-linoleyl, cholesteryl and glyceryl esters thereof) and their salts,dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionicacid and derivatives thereof (esters, ethers, peptides, lipids,nucleotides, nucleosides and salts) and sulfoximine compounds (forexample butionine sulfoximines, homocysteine sulfoximine, butioninesulfones, penta-, hexa- and hepta-thionine sulfoximine) in very smallcompatible dosages (for example pmol to μmol/kg), also (metal) chelators(for example α-hydroxyfatty acids, palmitic acid, phytic acid,lactoferrine), α-hydroxy acids (for example citric acid, lactic acid,malic acid), humic acid, bile acid, bile extracts, bilirubin,biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acidsand derivatives thereof (for example γ-linolenic acid, linoleic acid,oleic acid), folic acid and derivatives thereof, ubiquinone andubiquinol and derivatives thereof, vitamin C and derivatives thereof(for example ascorbyl palmitate, Mg ascorbyl phosphate, ascorbylacetate), tocopherols and derivatives (for example vitamin E acetate),vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoateof benzoin resin, rutinic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butyl hydroxyanisole, nordihydroguaiac resin acid,nordihydroguaiaretic acid, trihydroxy-butyrophenone, uric acid andderivatives thereof, mannose and derivatives thereof,Superoxid-Dismutase, zinc and derivatives thereof (for example ZnO,ZnSO₄), selenium and derivatives thereof (for example seleniummethionine), stilbenes and derivatives thereof (for example stilbeneoxide, trans-stilbene oxide) and derivatives of these active substancessuitable for the purposes of the invention (salts, esters, ethers,sugars, nucleotides, nucleosides, peptides and lipids).

Biogenic Agents

[0059] In the context of the invention, biogenic agents are, forexample, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbicacid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol,panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essentialoils, plant extracts and vitamin complexes.

Deodorants and Germ Inhibitors

[0060] Cosmetic deodorants counteract, mask or eliminate body odors.Body odors are formed through the action of skin bacteria on apocrineperspiration which results in the formation of unpleasant-smellingdegradation products. Accordingly, deodorants contain active principleswhich act as germ inhibitors, enzyme inhibitors, odor absorbers or odormaskers. Basically, suitable germ inhibitors are any substances whichact against gram-positive bacteria such as, for example,4-hydroxybenzoic acid and salts and esters thereof,N-(4-chlorophenyl)-N′-(3,4-dichlorophenyl)-urea,2,4,4′-trichloro-2′-hydroxydiphenylether (triclosan),4-chloro-3,5-dimethylphenol,2,2′-methylene-bis-(6-bromo-4-chlorophenol),3-methyl-4-(1-methylethyl)-phenol, 2-benzyl-4-chlorophenol,3-(4-chlorophenoxy)-propane-1,2-diol, 3-iodo-2-propinyl butyl carbamate,chlorhexidine, 3,4,4′-trichlorocarbanilide (TTC), antibacterialperfumes, thymol, thyme oil, eugenol, clove oil, menthol, mint oil,farnesol, phenoxyethanol, glycerol monocaprate, glycerol monocaprylate,glycerol monolaurate (GML), diglycerol monocaprate (DMC), salicylicacid-N-alkylamides such as, for example, salicylic acid-n-octyl amide orsalicylic acid-n-decyl amide.

[0061] Suitable enzyme inhibitors are, for example, esterase inhibitors.Esterase inhibitors are preferably trialkyl citrates, such as trimethylcitrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and,in particular, triethyl citrate (Hydagen® CAT, Cognis GmbH, Dusseldorf,FRG). Esterase inhibitors inhibit enzyme activity and thus reduce odorformation. Other esterase inhibitors are sterol sulfates or phosphatessuch as, for example, lanosterol, cholesterol, campesterol, stigmasteroland sitosterol sulfate or phosphate, dicarboxylic acids and estersthereof, for example glutaric acid, glutaric acid monoethyl ester,glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester,adipic acid diethyl ester, malonic acid and malonic acid diethyl ester,hydroxycarboxylic acids and esters thereof, for example citric acid,malic acid, tartaric acid or tartaric acid diethyl ester, and zincglycinate.

[0062] Suitable odor absorbers are substances which are capable ofabsorbing and largely retaining the odor-forming compounds. They reducethe partial pressure of the individual components and thus also reducethe rate at which they spread. An important requirement in this regardis that perfumes must remain unimpaired. Odor absorbers are not activeagainst bacteria. They contain, for example, a complex zinc salt ofricinoleic acid or special perfumes of largely neutral odor known to theexpert as “fixateurs” such as, for example, extracts of ladanum orstyrax or certain abietic acid derivatives as their principal component.Odor maskers are perfumes or perfume oils which, besides theirodor-masking function, impart their particular perfume note to thedeodorants. Suitable perfume oils are, for example, mixtures of naturaland synthetic perfumes. Natural perfumes include the extracts ofblossoms, stems and leaves, fruits, fruit peel, roots, woods, herbs andgrasses, needles and branches, resins and balsams. Animal raw materials,for example civet and beaver, may also be used. Typical syntheticperfume compounds are products of the ester, ether, aldehyde, ketone,alcohol and hydrocarbon type. Examples of perfume compounds of the estertype are benzyl acetate, p-tert.butyl cyclohexylacetate, linalylacetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.Ethers include, for example, benzyl ethyl ether while aldehydes include,for example, the linear alkanals containing 8 to 18 carbon atoms,citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde,hydroxy-citronellal, lilial and bourgeonal. Examples of suitable ketonesare the ionones and methyl cedryl ketone. Suitable alcohols are anethol,citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethylalcohol and terpineol. The hydrocarbons mainly include the terpenes andbalsams. However, it is preferred to use mixtures of different perfumecompounds which, together, produce an agreeable fragrance. Othersuitable perfume oils are essential oils of relatively low volatilitywhich are mostly used as aroma components. Examples are sage oil,camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil,lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanumoil, ladanum oil and lavendin oil. The following are preferably usedeither individually or in the form of mixtures: bergamot oil,dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol,α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde,linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice,citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal,lavendin oil, clary oil, β-damascone, geranium oil bourbon, cyclohexylsalicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldeingamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide,romilat, irotyl and floramat.

Preservatives

[0063] Suitable preservatives are, for example, phenoxyethanol,formal-dehyde solution, parabens, pentanediol or sorbic acid and theother classes of compounds listed in Appendix 6, Parts A and B of theKosmetikverordnung (A Cosmetics Directive≅).

Perfume Oils

[0064] Suitable perfume oils are mixtures of natural and syntheticperfumes. Natural perfumes include the extracts of blossoms (lily,lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves(geranium, patchouli, petitgrain), fruits (anise, coriander, caraway,juniper), fruit peel (bergamot, lemon, orange), roots (nutmeg, angelica,celery, cardamom, costus, iris, calmus), woods (pinewood, sandalwood,guaiac wood, cedarwood, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), needles and branches (spruce, fir, pine, dwarfpine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum,opoponax). Animal raw materials, for example civet and beaver, may alsobe used. Typical synthetic perfume compounds are products of the ester,ether, aldehyde, ketone, alcohol and hydrocarbon type. Examples ofperfume compounds of the ester type are benzyl acetate, phenoxyethylisobutyrate, p-tert.butyl cyclohexylacetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzylformate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate,styrallyl propionate and benzyl salicylate. Ethers include, for example,benzyl ethyl ether while aldehydes include, for example, the linearalkanals containing 8 to 18 carbon atoms, citral, citronellal,citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal,lilial and bourgeonal. Examples of suitable ketones are the ionones,α-isomethylionone and methyl cedryl ketone. Suitable alcohols areanethol, citronellol, eugenol, isoeugenol, geraniol, linalool,phenylethyl alcohol and terpineol. The hydrocarbons mainly include theterpenes and balsams. However, it is preferred to use mixtures ofdifferent perfume compounds which, together, produce an agreeableperfume. Other suitable perfume oils are essential oils of relativelylow volatility which are mostly used as aroma components. Examples aresage oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leafoil, lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil,galbanum oil, ladanum oil and lavendin oil. The following are preferablyused either individually or in the form of mixtures: bergamot oil,dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol,α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde,linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice,citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal,lavendin oil, clary oil, β-damascone, geranium oil bourbon, cyclohexylsalicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldeingamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide,romillat, irotyl and floramat.

Dyes

[0065] Suitable dyes are any of the substances suitable and approved forcosmetic purposes as listed, for example, in the publication“Kosmetische Färbemittel” of the Farbstoffkommission der DeutschenForschungs-gemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106.These dyes are normally used in concentrations of 0.001 to 0.1% byweight m/m, based on the mixture as a whole.

EXAMPLES

[0066] Microemulsions were prepared to the formulations shown inTable 1. To this end, the oil-soluble constituents were heated to 70-80°C. and melted, the water phase heated to the same temperature was partlyincorporated by stirring in the oil phase together with thewater-soluble constituents and the formulation was cold-stirred. Theviscosity of the formulations was determined by measurement with aBrookfield RVF viscosimeter with a Helipath TF spindle at 23° C./4r.p.m. TABLE 1 Influence of aluminium-zirconium salt on the viscosity ofmicroemulsions based on sugar surfactants, comparison formulation C1 andformulations 1 to 4 according to the invention; quantities of theconstituents in % m/m C1 1 2 3 4 INCI Name Decyl Glucoside 15 15 15 1515 Glyceryl Oleate 8 8 8 8 8 Dioctylcyclohexane 11 11 7 — 6Cyclomethicone 11 11 8 11 8 Dioctyl carbonate — — — 11 — Dicaprylylether— — 7 — 6 Aluminium Chlorohydrate 20 — — — — Aluminium Zirconium — 20 2020 20 Tetrachlorohydrex GLY PEG-120 Methylglucosedioleate — — — — 2Water to 100 to 100 to 100 to 100 to 100 Properties Appearance ClearClear Clear Clear Clear Viscosity (mPas) 6000 825000 875000 8500002300000

1. High-viscosity microemulsions containing: A) sugar surfactants, B)oil components and C) aluminium-zirconium salts.
 2. Microemulsions asclaimed in claim 1, characterized in that they have a Brookfieldviscosity (RVT viscosimeter, 23° C., 4 rpm, spindle TF Helipath) of atleast 100,000 mpas.
 3. Microemulsions as claimed in claims 1 and/or 2,characterized in that they contain sugar surfactants selected from thegroup consisting of A1) alkyl (and/or alkenyl) oligoglycosides and A2)fatty acid-N-alkyl polyhydroxyalkyl amides as constituents. 4.Microemulsions as claimed in at least one of claims 1 to 3,characterized in that they contain alkyl and/or alkenyl oligoglycosidescorresponding to formula (I): R¹O-[G]_(p)  (I) in which R¹ is an alkyland/or alkenyl group containing 4 to 22 carbon atoms, G is a sugar unitcontaining 5 or 6 carbon atoms and p is a number of 1 to 10, ascomponent (A1).
 5. Microemulsions as claimed in at least one of claims 1to 4, characterized in that they contain fatty acid-N-alkylpolyhydroxyalkylamides corresponding to formula (II):

in which R²CO is an aliphatic acyl group containing 6 to 22 carbonatoms, R³ is an alkyl or hydroxyalkyl group containing 1 to 4 carbonatoms and [Z] is a linear or branched polyhydroxyalkyl group containing3 to 12 carbon atoms and 3 to 10 hydroxyl groups, as component (A2). 6.High-viscosity microemulsions as claimed in at least one of claims 1 to5, characterized in that they contain as component B oil componentsselected from the group consisting of Guerbet alcohols based on fattyalcohols containing 6 to 18 carbon atoms, esters of linear C₆₋₂₀ fattyacids with linear C₆₋₂₀ fatty alcohols, esters of branched C₆₋₁₃carboxylic acids with linear C₆₋₂₀ fatty alcohols, esters of linearC₆₋₁₈ fatty acids with branched alcohols, esters of linear and/orbranched fatty acids with polyhydric alcohols and/or Guerbet alcohols,esters of hydroxycarboxylic acids with linear or branched C₆₋₂₂ fattyalcohols, triglycerides based on C₆₋₁₀ fatty acids, esters of C₆₋₂₂fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids,dicarboxylic acid esters, vegetable oils, branched primary alcohols,substituted cyclohexanes, linear and branched C₆₋₂₂ fatty alcoholcarbonates, Guerbet carbonates, esters of benzoic acid with linearand/or branched C₆₋₂₂ alcohols, linear or branched, symmetrical ornonsymmetrical dialkyl ethers containing 6 to 22 carbon atoms per alkylgroup, ring opening products of epoxidized fatty acid esters withpolyols, silicone oils and/or aliphatic or naphthenic hydrocarbons. 7.Microemulsions as claimed in at least one of claims 1 to 6,characterized in that they contain as component C aluminium-zirconiumsalts selected from the group consisting of aluminium-zirconiumtrichlorohydrate, aluminium-zirconium tetrachlorohydrate,aluminium-zirconium pentachlorohydrate, aluminium-zirconiumoctachlorohydrate and complex compounds thereof.
 8. Microemulsions asclaimed in at least one of claims 1 to 7, characterized in that theycontain thickeners as an optional component.
 9. Microemulsions asclaimed in at least one of claims 1 to 8, characterized in that theycontain A) 1-40% m/m sugar surfactants, B) 10-50% m/m oil components, C)5-40% m/m aluminium-zirconium salts, D) 0-10% m/m thickeners, with theproviso that the quantities shown add up to 100% m/m, optionally withwater and/or other typical auxiliaries and additives.
 10. The use of thehigh-viscosity emulsions claimed in claim 1 for the production ofcosmetic gel and stick formulations.